CN101296874A - Process for producing spherical inorganic particle - Google Patents
Process for producing spherical inorganic particle Download PDFInfo
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- CN101296874A CN101296874A CNA2006800297045A CN200680029704A CN101296874A CN 101296874 A CN101296874 A CN 101296874A CN A2006800297045 A CNA2006800297045 A CN A2006800297045A CN 200680029704 A CN200680029704 A CN 200680029704A CN 101296874 A CN101296874 A CN 101296874A
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- Prior art keywords
- spheroidal particle
- particle
- crushed products
- acid
- silicate
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- 238000000034 method Methods 0.000 title claims abstract description 78
- 239000010954 inorganic particle Substances 0.000 title claims abstract description 24
- 230000008569 process Effects 0.000 title claims abstract description 9
- 239000002245 particle Substances 0.000 claims abstract description 147
- 239000011521 glass Substances 0.000 claims abstract description 71
- 239000000463 material Substances 0.000 claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002253 acid Substances 0.000 claims abstract description 36
- 238000010306 acid treatment Methods 0.000 claims abstract description 33
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 19
- 239000011147 inorganic material Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims description 50
- 229910000077 silane Inorganic materials 0.000 claims description 43
- 239000003365 glass fiber Substances 0.000 claims description 37
- -1 silane compound Chemical class 0.000 claims description 32
- 238000001816 cooling Methods 0.000 claims description 24
- 238000004519 manufacturing process Methods 0.000 claims description 21
- 238000002347 injection Methods 0.000 claims description 19
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- 229910000272 alkali metal oxide Inorganic materials 0.000 claims description 9
- 125000000962 organic group Chemical group 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000000576 coating method Methods 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 238000010298 pulverizing process Methods 0.000 abstract description 33
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- 239000000945 filler Substances 0.000 abstract description 21
- 229910052814 silicon oxide Inorganic materials 0.000 abstract description 5
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- 238000005507 spraying Methods 0.000 abstract description 2
- 239000012798 spherical particle Substances 0.000 abstract 5
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- 239000003513 alkali Substances 0.000 description 7
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- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 3
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- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 2
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- PFRGGOIBYLYVKM-UHFFFAOYSA-N 15alpha-hydroxylup-20(29)-en-3-one Natural products CC(=C)C1CCC2(C)CC(O)C3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 PFRGGOIBYLYVKM-UHFFFAOYSA-N 0.000 description 1
- 125000000022 2-aminoethyl group Chemical group [H]C([*])([H])C([H])([H])N([H])[H] 0.000 description 1
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 1
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- 206010061218 Inflammation Diseases 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- 240000005373 Panax quinquefolius Species 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- SOKRNBGSNZXYIO-UHFFFAOYSA-N Resinone Natural products CC(=C)C1CCC2(C)C(O)CC3(C)C(CCC4C5(C)CCC(=O)C(C)(C)C5CCC34C)C12 SOKRNBGSNZXYIO-UHFFFAOYSA-N 0.000 description 1
- 229910052776 Thorium Inorganic materials 0.000 description 1
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- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- GAURFLBIDLSLQU-UHFFFAOYSA-N diethoxy(methyl)silicon Chemical compound CCO[Si](C)OCC GAURFLBIDLSLQU-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 description 1
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 description 1
- SBRXLTRZCJVAPH-UHFFFAOYSA-N ethyl(trimethoxy)silane Chemical compound CC[Si](OC)(OC)OC SBRXLTRZCJVAPH-UHFFFAOYSA-N 0.000 description 1
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- 238000007667 floating Methods 0.000 description 1
- 230000004054 inflammatory process Effects 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
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- 239000013528 metallic particle Substances 0.000 description 1
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- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
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- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 description 1
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
- Glass Compositions (AREA)
Abstract
A process for producing spherical inorganic particles which have high flowability, can be incorporated in a high proportion, and are useful as a filler for composite substrates such as printed wiring boards and encapsulating materials. Also provided is a process for producing spherical inorganic particles which have high flowability and can be incorporated in a high proportion and which are useful as a filler for encapsulating materials and give an encapsulating material having high electrical insulating properties. One of the processes for producing spherical inorganic particles comprises: (a1) pulverizing a silicon-oxide-containing inorganic material to form a pulverization product; (b1) heating the pulverization product in an atomized state to form the pulverization product into spherical particles; (c1) spraying water over the spherical particles to cool them while maintaining the atomized state of the spherical particles; and (d1) collecting the spherical particles. The other process, which is for producing spherical glass particles, comprises: a pulverization step in which a silicon-oxide-containing vitreous material is pulverized to form a pulverization product; an acid treatment step in which the pulverization product is contacted with an acid; and a sphering step in which the pulverization product is heated in a suspended state and formed into spherical particles.
Description
Technical field
The present invention relates to produce the method for spherical inorganic particle.
Background technology
Used inorganic particle, the inorganic particle that for example contains silicate as matrix material for example the filler of printed-wiring board (PWB) and packaged material to improve their size accuracies, thermotolerance etc.Sometimes use the glass fibre of pulverizing as inorganic particle, because they have even composition and can handle easily to reduce coarse grained ratio.Yet when containing a high proportion of glass fibre as filler in resin, the glass fibre of pulverizing is easy to become has length/diameter usually than high column, therefore, and in the remarkable resin flow that reduces of the viscosity increase of melting point resin.Therefore, they are as the filler that contains at high proportion, and its application is restricted.In addition, their dispersivenesses in resin also are nowhere near.
Have the inorganic particle that uniform-dimension distributes in order to produce, for example patent documentation 1 discloses by in container the glass fibre of pulverizing being exerted pressure and has produced the method for glass powder, and this powder contains the particle of the too high or too low length-to-diameter ratio of limited extent.Yet this technology is difficult to produce spheroidal particle, because they are broken under mechanical pressure on being positioned at other particle the time.Therefore, when they when mixing at high proportion, far can not be as the filler that can keep the resin good flow.
Patent documentation 2 is disclosed in behind the glass fibre coating tetraalkoxysilane, by it is pulverized the method for the sharp-pointed thin glass particle of production distribution of sizes.This technology also is difficult to produce spheroidal particle, when using in the patent documentation 1 disclosed technology, when they when mixing at high proportion, far can not be as the filler that can keep the resin good flow.
For production spherical metal oxide particle, patent documentation 3 discloses a kind of method, wherein will as raw-material metal-powder for example silicon metal powder drop in the chemical flame to form metallic particles, its blast synthesizing superfine oxide particle, for example silica dioxide granule with atomizing state.Yet this method comprises danger and cost height.
In order to produce spheroidal particle by glass fibre, for example patent documentation 4 discloses the method for handling as raw-material glass fibre, wherein be coated with organic materials for example the glass fibre of binding agent after pulverizing, drop in the flame nodularization glassy substances, simultaneously after-flame organic-containing materials.Yet this method is difficult to complete after-flame organic substance, because do not take cooling energetically, is easy to make the spheroidal particle of generation to reunite mutually once more, changes composite particles into.
Yet, develop the living glass powder that this technology is used for producing recycling at first, wherein reclaim the glass fibre that exhausted is coated with organic substance and reuse as industrial raw material.The broken glass powder of Sheng Chaning needs the processing of organism etc. with the manufacture product after all by this method.
In order to produce the spherical glass particle, patent documentation 5 discloses a kind of method, wherein as the melten glass of raw material from nozzle ejection to the continuous flow that flows downward to change glass drop into, it breaks away from downward path and is recovered in the accumulator tank.
In order to produce the spherical glass particle, patent documentation 6 discloses a kind of method, wherein will give birth to glass material and put into and contain fusion and nodularization in the oxygen plasma.
In order to produce the spherical glass particle, patent documentation 7 discloses a kind of method, wherein (regulates it and consists of and have very concrete final glass and form, for example contain the SiO of 2-15 weight % as the solution that contains different mixtures of frit or colloidal sol
2) be injected in the flame, what quenching obtained then carefully drips.The product of this method can have concrete purposes, for example produces the insulating film of intermediate layer be used for photolithographic fluorescence display and as the thin glass film of substrate.
Patent documentation 8 discloses a kind of production spherical glass particulate method, and is similar with patent documentation 7 disclosed methods basically, consists of and contains 40-70 weight %SiO except controlling final glass
2To improve the resin flow of wherein mixing spheroidal particle.Spherical glass particle as the finished product can have concrete purposes, for example produces the thin glass film as substrate, as using the spherical glass particulate situation of being produced by the method for patent documentation 7.
On the other hand, patent documentation 9 discloses a kind of composition that is used for high strength glass fiber, and it contains the SiO of certain content
2, Al
2O
3With MgO and be substantially free of basic metal, can in the short fusion time, produce and be substantially devoid of tubular fibre.
In order to use the acid treatment glass fibre, patent documentation 10 discloses a kind of method of handling the E-glass fibre with aqueous acid and has contained the upper layer of high-content silicon oxide with formation, improves the resistance toheat of fiber thus, and does not sacrifice the performance of E-glass fibre.
Also be in order to use the acid treatment glass fibre, patent documentation 11 discloses a kind of production method of woven fiber glass of special E-glass composition, wherein the woven fiber glass that E-glass is formed immerse in the acetic acid aqueous solution with alkaline-earth metal and basic metal elution in solution, therefore their content is reduced to based on the 20ppm of woven fiber glass or lower.
In order to use the acid treatment silica dioxide granule, patent documentation 12 discloses a kind of method, wherein the burning metallic silicon particle has the silica dioxide granule that mean diameter is 0.01-10 μ m with formation in oxygen flow, with the lower concentration mineral acid particle that clean to obtain of the aqueous solution of nitric acid for example, to remove radioelement compound, for example uranium compound.
In order to handle metallic silicon particle, patent documentation 13 discloses a kind of method, wherein with inorganic acid aqueous solution clean metal silicon grain to remove radioelement, for example uranium and thorium, up to 1ppb or lower, the particle that burn processing is crossed in oxygen flow is to produce the silica dioxide granule that highly purified mean diameter is 0.01-10 μ m.
Patent documentation 1:JP-A-4-338133
Patent documentation 2:JP-A-2003-192387
Patent documentation 3:JP-B-1-55201
Patent documentation 4:JP-A-11-228164
Patent documentation 5:JP-A-2005-179145
Patent documentation 6:JP-A-2004-338961
Patent documentation 7:JP-A-8-310836
Patent documentation 8:JP-A-8-91874
Patent documentation 9:JP-A-11-21147
Patent documentation 10:JP-A-7-172876
Patent documentation 11:JP-A-2001-73253
Patent documentation 12:JP-B-7-61855
Patent documentation 13:JP-B-7-61856
Summary of the invention
In many cases with organic silane compound to as matrix material for example the inorganic particle of the filler of printed-wiring board (PWB) and packaged material carry out silane treatment to improve product performance.
The method of using organic silane compound to carry out silane treatment comprises (1) after the glass fibre as filler material immerses in the aqueous solution that contains organic silane compound, the pulverizing glass fibre; (2) after the glass fibre as filler material is ground into than fine particle, impregnated glass fiber; (3) after the glass fibre as filler material is ground into than fine particle, glass fibre and organic silane compound and material resin are carried out kneading.
Method (1) relates to the problem that is caused by insufficient processing, because the glass fibre of pulverizing not is to be handled by organic silane compound fully, leaves the face of untreated pulverizing.When the glass particle drying of silane treatment was composite particles, method (2) was easy to cause their reunion.Method (3) can reduce the efficient that silane adds, because the linked reaction of organic silane compound is insufficient, causes forming inadequate chemical bond.
When being used for printed-wiring board (PWB) laminated plate filler, the glass particle with the composition that is commonly referred to non-alkali glass does not have big problem.Yet they contain trace basic metal, and when being used from packaged material with resin one, electrical isolation capabilities is not as the silicon oxide particle of alkali metal-free.Therefore, wish to improve them and be used for the performance of packaged material.
In addition, the fusing point of non-alkali glass is lower than silicon-dioxide, and spheroidized particle has real circular cross section basically.When they are made by the glass fibre of pulverizing, their easier control particle diameters and being dispersed in better in the resin so that mix flow is better, so can obtain to mix particulate pressed compact as filler with higher proportion.
A first aspect of the present invention solves the problems referred to above that relate in the routine techniques, and the method that is more suitable for as the spherical inorganic particle of filler of making is provided.
Of the present invention second to fourth aspect, also solve the problems referred to above that relate in the routine techniques, the method that is more suitable for as the spherical inorganic particle of packaged material filler of making is provided, wherein they mix to improve the electrical insulation capability of packaged material with resin, keep allowing their spherical non-alkali glass particulate characteristics to mix at high proportion simultaneously.
The first aspect present invention that addresses the above problem provides the method for making spherical inorganic particle, comprises the following steps:
(a1) pulverizing contains the inorganic materials of silicate to form crushed products;
(b1) crushed products of heating levitated state is to change crushed products into spheroidal particle;
(c1) injection water keeps the atomizing state of spheroidal particle simultaneously with the cooling spheroidal particle on spheroidal particle; And
(d1) collect the refrigerative spheroidal particle.
The inorganic materials of pulverizing in step (a1) that contains silicate is preferably vitreous, fibers form particularly, and agent coated in order to apply.
The water that uses in step (c1) preferably contains organic silane compound.
The second aspect present invention that addresses the above problem provides and makes spherical glass particulate method, comprises the following steps:
(a2) pulverize the vitreous material that contains silicate and contain 1.0 weight % or alkalimetal oxide still less, form crushed products;
(b2) crushed products of heating levitated state changes crushed products into spheroidal particle; With
(d2) spheroidal particle is contacted with acid, form the acid-treated spheroidal particle in surface.
Preferably comprise step (c2) in step (b2) with (d2), promptly injection water on spheroidal particle cools off spheroidal particle, keeps the levitated state of spheroidal particle simultaneously.
Preferably with the vitreous material that contains silicate of form of glass fibers.
The present invention third and fourth aspect that addresses the above problem provides and makes spherical glass particulate method, comprises the following steps:
(a3) will contain 1.0 weight % or still less the vitreous material that contains silicate of alkalimetal oxide contact to form surperficial with the acid-treated vitreous material that contains silicate with acid;
(b3) vitreous material that contains silicate of comminution surface processing is to form crushed products; And
(c3) crushed products of heating levitated state changes crushed products into spheroidal particle.
A fourth aspect of the present invention provides makes spherical glass particulate method, comprises the following steps:
(a4) pulverize and to contain the 1.0 weight % or the vitreous material that contains silicate of alkalimetal oxide still less, form crushed products;
(b4) crushed products is contacted with acid, form the acid-treated crushed products in surface, and
(c4) the surface-treated crushed products of heating levitated state changes the surface-treated crushed products into spheroidal particle.
The vitreous material that contains silicate that is used for third and fourth aspect is preferably with form of glass fibers.
In addition, third and fourth aspect in step (c3) and (c4) all preferably includes step (d3) and (d4) after separately, sprays the water that contains organic silane compound on spheroidal particle, and the cooling spheroidal particle keeps the levitated state of spheroidal particle simultaneously.
The invention effect
First aspect
Inorganic particle by the first aspect present invention manufacturing is spherical basically, therefore has high workability as resin extender, can be to mix at high proportion and evenly.Be cooled by the spheroidal particle that is injected in the water heating on them, keep atomizing state simultaneously, in manufacturing system, do not need other cooling zone.In addition, the cooling spheroidal particle keeps atomizing state (buoyant state) to be agglomerated into composite particles mutually to stop simultaneously.In addition, by spray keeping pyritous water cooling particle, therefore drying when reclaiming the refrigerative spheroidal particle does not need other drying step.
The organic materials that contains silicate as raw material is preferably vitreous, because the product spherical inorganic particle has height spheric cross section.Use glass fibre can produce the spherical inorganic particle of relative uniform grading.In other words, fiber is owing to only change in lengthwise dimension, thus can fully pulverize the generation spheroidal particle, because they have uniform diameter basically.Another advantage of using glass fibre is that the content of volatiles in the product spherical inorganic particle is relatively low, because fiber carries out nodularization after fusion.
In addition, be used as the inorganic materials that contains silicate of the raw material of first aspect present invention method, preferably not coated dose, for example organic reagent, protective agent, sizing agent coatings such as (sizing agent).When not coated, be easy to form in the short period of time required milling product.For example, uncoated raw material can fully be pulverized in about 1 hour and be the particle of uniform-dimension basically.The particle that applies with its contrast needs about 5 hours so that the crushed products of size much at one to be provided.
When the water that contains organic compound when preferred usefulness sprayed, containing the spheroidal particle that the inorganic materials of silicate forms by pulverizing can apply with organic compound fully.This disappears except when raw material applies inadequate shortcoming with organic silane compound when containing the jet of water of organic silane compound before pulverizing.In addition, spheroidal particle preferably by cooling off with the jet of water that contains organic silane compound, keeps atomizing state, because this can stop them to be agglomerated into composite particles mutually simultaneously.In other words, even when their subsequent dewaterings and drying, only dipping contains the inorganic materials of silicate and does not carry out injection water and may make them be agglomerated into composite particles in containing the water of organic silane compound, and generation should be pulverized them once more to guarantee the shortcoming of given particle diameter.
Second aspect
The vitreous material that contains silicate as the raw material of second aspect present invention method has low relatively fusing point.Therefore, the spherical glass particle of producing by the second aspect method has circular basically cross section, and is mobile high, and can be as filler to mix in the resin at high proportion.In addition, the vitreous material that contains silicate as raw material contains 1.0 weight % or alkalimetal oxide still less, remove for example spheroidal particle as crushed products of basic metal and alkaline-earth metal ions of metal ion with acid treatment with elution from vitreous material, can significantly improve them and mix the electrical insulation capability of packaged material wherein with resin.
Described method is brought another advantage, and promptly the content of volatiles is low relatively in the spherical glass particle, because carry out nodularization after the inorganic materials that contains silicate by fusion is made vitreous material.
In the method for second aspect present invention, when the particle maintenance simultaneously of injection water on spheroidal particle afloat, can cool off spheroidal particle effectively for water.
In addition, when preparing particle by the glass fibre with substantially the same diameter, this method can reduce the ratio of thick spheroidal particle, because particle is easy to pulverize on cross-wise direction.
Third and fourth aspect of the present invention
Fusing point as the vitreous material that contains silicate of the raw material of the present invention's third and fourth aspect method is low relatively.Therefore, the spherical glass particle by these method manufacturings has circular basically cross section, and is mobile high and can be as filler to mix in the resin at high proportion.In addition, the vitreous material that contains silicate as raw material contains 1.0 weight % or alkalimetal oxide still less, handle with elution from vitreous material with acid and to remove for example spheroidal particle as crushed products of basic metal and alkaline-earth metal ions of metal ion, can significantly improve them and mix the electrical insulation capability of packaged material wherein with resin.
In addition, these methods are brought another advantage, and promptly the content of volatiles is low relatively in the spherical glass particle, because carry out nodularization after the inorganic materials that contains silicate by fusion is made vitreous material.
In addition, when producing particle by the glass fibre with substantially the same diameter, these methods can reduce the ratio of thick spheroidal particle, because they are easy to pulverize on cross-wise direction.
In addition, when with the jet of water cooling that contains organic silane compound and when keeping afloat simultaneously, can cool off the spheroidal particle that adds thermosetting simultaneously and handle, stop particle agglomeration to become composite particles simultaneously with silane compound.When at high temperature spraying with the water that contains organic silane compound, particle drying when reclaiming the refrigerative spheroidal particle need not to have additional drying step.
Description of drawings
Fig. 1 is system overview figure, promptly is used to implement the test macro that has air furnace of an embodiment of method of the present invention.
Fig. 2 represents the scanning electron microscope Photomicrograph with the spherical inorganic particle of an embodiment manufacturing of method of the present invention; (a) crushed products of E-glass fibre and (b) spherical E-glass particle.
Fig. 3 represents the scanning electron microscope Photomicrograph with the spherical inorganic particle of the method manufacturing of a first aspect of the present invention; (a) crushed products of crystalline silica and (b) the unsetting silicon oxide particle of spheric.
Reference numeral is described
1 powder as crushed products
2 hold-up vessels
3 powder material feeders
4 burning gases
5 fuel gas
6 carrier gas
7 burners
8 stoves
9 melting zones
10 cooling sprays
11 deep bed filter
12 vacuum fans
13 tubing systems
Embodiment
A first aspect of the present invention
The inorganic materials that contains silicate as the raw material of first aspect present invention method is preferably vitreous, and more preferably non-alkali glass further more preferably contains the non-alkali glass of 50 weight % or more silicon-dioxide.
Consider the fibers form of the preferably about 3-30 μ of vitreous material m diameter from the angle of easy pulverizing.
In addition, when use is coated with the inorganic materials that contains silicate that applies agent as the raw material of the inventive method, preferably after removing the coating agent, pulverizing by processing such as calcinings.
Can by currently known methods for example ball milling carry out pulverising step (a1).For example, the crushed products particle has the median size of about 20 μ m, although be not restricted to this.Can form 1 μ m or more minor diameter than fine particle.
The step (b1)-(d1) that can be undertaken by system is as shown in Figure 1 subsequently handled the crushed products of making by step (a1).With reference to figure 1 these steps are described.
In step (b1) (nodularization step), handle the crushed products 1 that forms by step (a1) (pulverising step), wherein for example by powder generator 3, for example table feeder, screw feeder, ultrasonic nebulizer etc., the product 1 that is stored in the hold-up vessel 2 is dropped into melting zone 9 stove 8 by carrier gas 6 from the top, make the product particle keep atomizing (floating) state.
Carrier gas 6 can be nitrogen, air or oxygen, or considers the gas of the burning 4 that is preferred for describing later from working efficiency.When considering explosion hazard, preferably use nitrogen.
In step (b1) (nodularization step), by the flame heating crushed products of burning together and producing with gas 4 air or oxygens by fuel gas 5 and burning in the burner 7.Fuel gas 5 is LPG gas (propane gas) preferably.
In the melting zone 9 of stove, can use air particle to be heated to about 1500-2000 ℃, or be heated to about 2400-3000 ℃ by the oxygen burner that uses oxygen as the air burner that burns with gas 4.If desired, when fuel gas 5 burnt with oxygen, water-cooled cooling zone (not shown) can be arranged near the bottom of stove 8, is used for the preliminary cooling of later step (c1) (cooling step).
Heating makes crushed products 1 change spheroidal particle into.
The particle that adds thermosetting in step (c1) with water cooling in stove in the melting zone 9, promptly when they fell, for example the cooling spray 10 by the spout ejection that is arranged on the stove bottom cooled off.This step makes spheroidal particle be cooled to lesser temps, for example about 160 ℃, collects in later step (d1) simultaneously.They also can dewater.
In step (c1), the water of injection preferably contains the organic silane compound of 0.01-3.0 weight %.How to contain also unrestricted.For example, may be dissolved in the water, spray the solution of gained then.Do not limit the kind of dissolved organic silane compound, some examples comprise the compound with hydrolysable group and hydrophobic group (organic group), for example known silane coupling agent that is used for glass fibre.
These silane coupling agents comprise the silane compound that is expressed from the next:
R
4-n-Si-(OR’)
n
Wherein R is an organic group; R ' is methyl, ethyl or propyl group; " n " is the integer of 1-3; R ' can be identical or different; " n " preferably 3.
Silane compound comprises the compound with unsaturated double-bond, vinyltriethoxysilane for example, vinyltrimethoxy silane and γ-(methacryloxypropyl) Trimethoxy silane; Compound with epoxy group(ing), for example β-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, γ-glycidyl oxygen propyl trimethoxy silicane and γ-glycidyl oxygen propyl group methyldiethoxysilane; Compound with sulfydryl, for example γ-Qiu Jibingjisanjiayangjiguiwan; With the compound with amino, for example γ-An Bingjisanyiyangjiguiwan, N-β (aminoethyl) γ-An Bingjisanjiayangjiguiwan and N-β-(N-vinyl benzene methyl aminoethyl)-γ-An Bingjisanjiayangjiguiwan.
In step (d1), in step (c1), can collect by powder recovering device with injection water refrigerative spheroidal particle.When using powder recovering device, collect the refrigerative spheroidal particle by cyclonic separator, deep bed filter, wet collector etc., it is outdoor wherein to use vacuum fan, gas blower etc. that gas is discharged as required.The combination of preferred cyclonic separator of powder recovering device and deep bed filter.
Of the present invention second to fourth aspect
More preferably be commonly called the glass of alkali-free E glass as the vitreous material that contains silicate of the raw material of the inventive method, it has and contains 0.8 weight % or the low alkali composition of sodium or potassium for example more.More preferably be commonly called the glass of S glass, it has and contains the 0.1 weight % or the alkali-metal composition of low levels more.The silicon-dioxide that further more preferably contains 50-70 weight %.The glass composition that dioxide-containing silica surpasses above-mentioned scope is difficult to produce vitreous material (particularly fiberglass) or is ground into the spheroidal particle of rounded section basically.
Representational E of the present invention and S glass composition have formation component and the performance that provides in the table 1.
Table 1
The unit of prescribed value and measured value is weight %.Determine B by the wet analysis method
2O
3And R
2The measured value of CaO during the measured value of O and S glass are formed.Determine the measured value of other compound by x-ray fluorescence analysis.
Consider that from easy angle break degree vitreous material is preferably with the fibers form of about 3-30 μ m diameter.
In addition, as preferably not coated dose of the vitreous material that contains silicate of the raw material of the inventive method, coatings such as for example organic surface-coated agent, protective agent, sizing agent.When not coated, be easy to form within a short period of time required crushed products.For example, uncoated raw material can fully be ground into the particle of uniform-dimension basically in about 1 hour.Need about 5 hours with its contrast coated raw material.When use is coated with the vitreous material that contains silicate during as raw material that applies agent, preferably after removing the coating agent, pulverizing by processing such as calcinings.
Can by known technology for example ball milling the vitreous material that the present invention contains silicate is pulverized.The crushed products particle has the median size of about 20 μ m, although be not restricted to this.Can form 1 μ m or more minor diameter than fine particle.
A second aspect of the present invention
The system shown in Fig. 1 be can utilize, nodularization step subsequently, the crushed products of using injection water refrigerative step (c2) (cooling step) processing to make as required carried out by pulverising step of the present invention.With reference to the description of this embodiment of figure 1 with as identical in the description of the first aspect present invention of preceding description, wherein acid treatment step is not expressed.
After carrying out the nodularization step, carry out cooling step, wherein use the spheroidal particle of injection water cooling gained, make them keep suspended state simultaneously by heating.More particularly, heat treated globulate particulate crushed products in melting zone 9 is cooled off, promptly when they fell, the cooling spray 10 that sprays by the spout that is arranged on lower furnace cooled off.This step makes spheroidal particle be cooled to for example about 150 ℃ of lower temperature, collects in later step (d1) simultaneously.They also can be dewatered fully.
Can be by collecting with injection water refrigerative spheroidal particle with the identical collector that uses in first aspect present invention, mode and process.
In the method for second aspect present invention, the refrigerative spheroidal particle is contacted with acid, preferably immerse in the acid to generate surface-treated spherical glass particle.The acid of using comprises for example organic acid and for example nitric acid, hydrochloric acid and the vitriolic mineral acid of acetate without limits, wherein more preferably strong acid.When using hydrochloric acid and sulfuric acid, can be respectively residual in the spherical glass particle have Cl and a S.When in the packaged material during still residual these elements, be unaccommodated, nitric acid does not have the unaccommodated resistates of pair packaged material because of residual, so be preferred.Can suitably set solution acid concentration, dipping temperature and the time that to flood spheroidal particle.When using nitric acid, its concentration is preferably 0.3-2.0N.The acid treatment elution is removed and is being contained the basic metal that exists on the inorganic material surface of silicate and alkaline-earth metal in some cases.In addition, preferably acid-treated particle is dewatered, and water cleans to remove the metal ion of elution.
In this manual, spheroidal particle only is called as " acid treatment " with contacting hereinafter of acid.
The acid-treated spherical glass particle of the inventive method manufacturing is preferably further handled (silane treatment) with organic silane compound.The kind of dissolved organic silane compound without limits.Some examples comprise the compound with hydrolysable group and hydrophobic group (organic group), for example known silane coupling agent that is used for glass fibre.
Second aspect can be used the silane coupling agent identical with first aspect.
Third and fourth aspect
In the method aspect of the present invention third and fourth, the refrigerative spheroidal particle is contacted with acid, preferably it is immersed in the acid.The acid of using comprises for example organic acid and for example nitric acid, hydrochloric acid and the vitriolic mineral acid of acetate without limits, wherein more preferably strong acid.When using hydrochloric acid and sulfuric acid, can be in the spherical glass particle residual respectively have C1 and a S.When still residual these elements in packaged material, be unaccommodated, nitric acid to the unaccommodated residue of packaged material, is preferred because of not residual therefore.Setting that can be suitable will be flooded solution acid concentration, dipping temperature and the time of spheroidal particle.When using nitric acid, concentration is preferably 0.3-2.0N.The acid treatment elution is removed and is being contained the basic metal that exists on the inorganic material surface of silicate and alkaline-earth metal in some cases.In addition, preferably acid-treated particle is dewatered, and water cleans to remove the metal ion of elution.
In this manual, spheroidal particle only is called as " acid treatment " with contacting hereinafter of acid.
A third aspect of the present invention is being pulverized it after with acid treatment the inorganic materials that contains silicate.This advantage of bringing is to have improved crush efficiency, because make material become frangible by acid treatment, is more suitable for pulverizing.
A fourth aspect of the present invention after the vitreous material that contains silicate is pulverized, uses acid to its processing.This advantage of bringing is to have improved acid treatment efficient, because increased specific surface area by pulverizing.
When the vitreous material that contains silicate was form of glass fibers, the present invention can further improve and pulverizes and acid treatment efficient.
Can utilize system shown in Figure 1 to carry out subsequently nodularization step and as required (d3) and (d4) crushed products made by pulverising step of the present invention of step process, wherein with the aqueous solution processing (d3) of the organic silane compound that sprays and (d4) spheroidal particle (hereinafter only being called as " silane treatment " or " silane treatment step " sometimes) of levitated state in the step.Identical with the description of previously described first aspect present invention by the description with reference to this embodiment of figure 1, wherein acid treatment step is not expressed.
In step (d3) with the silane treatment (d4),, can be undertaken by being used for carrying out after the nodularization step aqueous solution that refrigerative sprays although be not necessary for the present invention.Spheroidal particle can contact with the water that contains organic silane compound (cooling spray 10) that is sprayed by the spout that is arranged on lower furnace when they fall.This step makes spheroidal particle be cooled to for example about 150 ℃ of lesser temps, in later step, collects simultaneously, and dehydration.
In step (d3) with (d4), the aqueous solution of injection preferably contains the organic silane compound of 0.01-3.0 weight %.How to contain also unrestricted.For example, it may be dissolved in the water, sprays the resulting aqueous solution then.The kind of dissolved organic silane compound is also unrestricted.Some examples comprise the compound with hydrolysable group and hydrophobic group (organic group), for example known silane coupling agent that is used for glass fibre.
These steps can be used and the identical silane coupling agent in the present invention first and second aspects.
The spherical glass particle of the inventive method manufacturing can be collected by later step.For example, in the silane treatment step, can collect by collector, mode and process identical aspect the present invention first and second with injection water refrigerative spheroidal particle.
When being crushed at the present invention first raw material in fourth aspect that particularly weight average particle diameter is several microns, particle can block tubing system.Therefore, can be before pulverising step, afterwards or mix in the pulverising step weight average particle diameter be 1 μ m or littler than fine particle to prevent the problems referred to above.The average primary particle diameter of preferably mixing 1-5 weight % in crushed products is the thin silicate granules of 5-100nm.Can by at high temperature in the hydrogen-oxygen inflammation processing silicon chloride be hydrolyzed, remove de-chlorine hydride then and make thin silicate granules.
By embodiment the present invention is described.
A first aspect of the present invention
Embodiment 1
Softening temperature is the inorganic materials that 850 ℃ fiber E-glass conduct contains silicate, it is crushed to filament diameter is that 11 μ m and average fiber length are 21 μ m, be brought in the system shown in Figure 1 with 15kg/ hour by air, heat by air burner, injection water with the γ-glycidyl oxygen propyl trimethoxy silicane that contains 0.1 weight % cools off then, fiber keeps atomizing state simultaneously, and collects to make spherical E-glass particle by deep bed filter.
Embodiment 2
Softening temperature is 1700 ℃ a pulverizing crystalline silica (median size: 15 μ m) as the inorganic materials that contains silicate, be brought in the system with cooling zone shown in Figure 1 with 8kg/ hour by oxygen, heat by the oxygen burner, and cool off with the injection water of the γ that contains 0.1 weight %-glycidyl oxygen propyl trimethoxy silicane, particle remains on atomizing state simultaneously, and collects to make the spherical silica particle by deep bed filter.
Fig. 2 and 3 has represented the scanning electron microscope Photomicrograph of the spherical inorganic particle separately of manufacturing in embodiment 1 and 2, wherein (a) expression product of pulverizing and inorganic particle of (b) representing nodularization.Shown in Fig. 2 (b), the spherical E-glass particle of making in embodiment 1 has the height circular cross section, and median size is about 18 μ m and specific surface area is about 0.4m
2/ g.Shown in Fig. 3 (b), although have the relatively poor circular cross section of making than embodiment 1 of particle, the spherical silica particle median size of making in embodiment 2 is about 25 μ m, specific surface area is about 1.7m
2/ g.
Estimate
Made among the embodiment 1 and 2 that mixes 85 weight % the Resins, epoxy pressed compact of making as the spheroidal particle of filler.Each expresses high dimensional stability and moisture resistance energy.Even mix in 70 weight % embodiment 1 and 2 composition epoxy resin of each self filler of making, because the excessive increase of resin viscosity and can not castable.
Of the present invention second to fourth aspect
Embodiment 3
Use that to have the composition, the mean length that provide in the table 1 be the chopped strand of 850 ℃ fiber E-glass as 25mm and softening temperature, as the glassiness inorganic materials that contains silicate.
Is 25 μ m with their ball millings to median size, and is brought in the system shown in Figure 1 with 15kg/ hour by air, heats to make spheroidal particle by air burner then.
Then, they are flooded (500cc/20g sample) carried out acid treatment in 1 hour in 70 ℃ of 1.0N aqueous nitric acid, water cleans and dehydration then.
(1) before pulverising step, (2) after pulverising step and before the nodularization step, (3) carry out acid treatment after the nodularization step.
In order to measure specific conductivity, will immerse while stirring in the 100cc pure water through the 10g sample of pulverizing, acid treatment and nodularization step, measure steeping medium then.Think that the medium of high conductance contains the basic metal of the elution of high level, suppose that the material that goes out from the sample elution is a basic metal, so this sample contains the basic metal of high level.In table 2, provide the result.
Table 2
(1) after the acid treatment, pulverizes nodularization then (third aspect)
(2) after the pulverizing, carry out acid treatment, nodularization then (fourth aspect)
(3) after the pulverizing, carry out nodularization, acid treatment then (second aspect)
Embodiment 4
To make spheroidal particle with embodiment 3 same way as, except use has the chopped strand of the fiber S-glass that the given mensuration of table 1 forms as the vitreous material that contains silicate, the chopped strand that replaces fiber E-glass makes and with 0.5N aqueous nitric acid replacement 1.0N aqueous nitric acid.In table 2, provide the result.
Embodiment 5
Making spheroidal particle with embodiment 3 same way as, the chopped strand that has the fiber S-glass that the given mensuration of table 1 forms except use is replaced the chopped strand of fiber E-glass as the vitreous material that contains silicate.In table 2, provide the result.
Comparative example 1
To make spheroidal particle, except omitting acid treatment with embodiment 3 same way as.In table 2, provide the result.
Comparative example 2
To make spheroidal particle, except omitting acid treatment with embodiment 4 same way as.In table 2, provide the result.
Specific conductivity is estimated
When the acid treatment (embodiment 3-5), the spherical glass particle has the specific conductivity that reduces greatly, no matter is E-glass or S-glass, based on this, thinks that the alkaline components that exists advantageously and significantly removed by elution in the spherical glass particle.
Resin Flow is estimated
Observe flowability in the spherical glass particulate resin of in mixing embodiment 3-5 and comparative example 1 and 2, making and do not have significant difference.All these particles are spheric, think very little to the Resin Flow influence, and its flowability is mainly determined by particle shape.
Pulverize easy degree evaluation
The chopped strand of the S-glass fibre of the manufacturing of using in embodiment 4 or 5 carries out pulverizing before or after the acid treatment in the mode of describing with embodiment 3, wherein pulverizes the 100kg chopped strand 3 hours in having the 100L ball mill of 100kg ball.The median size of not carrying out acid-treated and acid-treated crushed products is respectively 9.6 μ m and 5.4 μ m, based on this, thinks that acid treatment helps the pulverizing of staple fibre.Yet, be noted that acid-treated particle has higher a little specific conductivity, as shown in table 2; (1): equal acid-treated product and (2): equal not acid-treated product.
The preparation of pressed compact
Silane treatment has been carried out in spheroidal particle (1) and (2) of making in embodiment 3, wherein spheroidal particle (1) and (2) have been cooled off with containing the injection water solution of 0.5 weight % as the aminopropyl triethoxysilane of silane compound.In addition, the spheroidal particle (3) of the acid treatment of making is also carried out silane treatment in embodiment 3, wherein spheroidal particle (3) is cooled off with containing the injection water solution of 0.5 weight % as the aminopropyl triethoxysilane of silane compound.The pressed compact of preparation Resins, epoxy, each all mixes the spherical glass particle that 80 weight % cross as the silane treatment of filler.Do not cause any problem during preparation.Yet, mix the particulate Resins, epoxy of making among the embodiment 3 and do not have enough flowabilities at melting point resin with acid treatment, can not make pressed compact.
Sum up
Consider the performance of desired product, should suitably set the order of pulverizing, nodularization and acid treatment step.
Industrial applicibility
By the spherical inorganic particle that comprises the spherical glass particle of the inventive method manufacturing, can be used for multiple Close for example filler of printed substrate and encapsulating material of sill.
Claims (15)
1. a method of making spherical inorganic particle comprises the following steps:
(a1) pulverize the inorganic materials that contains silicate, form crushed products;
(b1) crushed products of heating levitated state changes crushed products into spheroidal particle;
(c1) injection water keeps the atomizing state of spheroidal particle simultaneously with the cooling spheroidal particle on spheroidal particle; And
(d1) collect the refrigerative spheroidal particle.
2. according to the process of claim 1 wherein that the described inorganic materials that contains silicate is vitreous.
3. according to the method for claim 2, wherein said vitreous material is a fibers form.
4. according to each the method for claim 1-3, wherein contain the not coated dose coating of inorganic materials of silicate.
5. according to each the method for claim 1-4, wherein the water that uses in step (c1) contains organic silane compound.
6. according to the method for claim 5, wherein organic silane compound is expressed from the next:
R
4-n-Si-(OR’)
n
Wherein R is an organic group; R ' is methyl, ethyl or propyl group; N is the integer of 1-3.
7. make spherical glass particulate method for one kind, comprise the following steps:
(a2) pulverize the vitreous material contain silicate and to contain 1.0 weight % or alkalimetal oxide still less to form crushed products;
(b2) crushed products of heating levitated state changes crushed products into spheroidal particle; And
(d2) spheroidal particle is contacted with acid, form the spheroidal particle of surface with acid treatment.
8. produce spherical glass particulate method for one kind, comprise the following steps:
(a2) pulverize the vitreous material contain silicate and to contain 1.0 weight % or alkalimetal oxide still less to form crushed products;
(b2) crushed products of heating levitated state changes crushed products into spheroidal particle;
(c2) on spheroidal particle injection water with the cooling spheroidal particle, keep simultaneously spheroidal particle levitated state and
(d2) the refrigerative spheroidal particle is contacted to form the spheroidal particle of surface with acid treatment with acid.
9. according to the manufacturing spherical glass particulate method of claim 7 or 8, the vitreous material that wherein contains silicate is a form of glass fibers.
10. make spherical glass particulate method for one kind, comprise the following steps:
(a3) vitreous material that contains silicate and contain 1.0 weight % or alkalimetal oxide still less contact with acid, form the surperficial vitreous material that contains silicate with acid treatment;
(b3) vitreous material that contains silicate that comminution surface was handled is to form crushed products; And
(c3) crushed products of heating levitated state changes crushed products into spheroidal particle.
11. according to the manufacturing spherical glass particulate method of claim 10, the vitreous material that wherein contains silicate is a form of glass fibers.
12. manufacturing spherical glass particulate method according to claim 10 or 11, this method also comprises step (d3) afterwards in step (c3): the water that injection contains organic silane compound on spheroidal particle keeps the levitated state of spheroidal particle simultaneously with the cooling spheroidal particle.
13. make spherical glass particulate method, comprise the following steps: for one kind
(a4) pulverize the vitreous material contain silicate and to contain 1.0 weight % or alkalimetal oxide still less to form crushed products;
(b4) crushed products is contacted with acid, form the crushed products of surface with acid treatment, and
(c4) the surface-treated crushed products of heating levitated state changes surface-treated crushed products into spheroidal particle.
14. according to the manufacturing spherical glass particulate method of claim 13, the vitreous material that wherein contains silicate is a form of glass fibers.
15. manufacturing spherical glass particulate method according to claim 13 or 14, this method also comprises step (d4) afterwards in step (c4): the water that injection contains organic silane compound on spheroidal particle keeps the levitated state of spheroidal particle simultaneously with the cooling spheroidal particle.
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| JP2005236450A JP4941629B2 (en) | 2005-08-17 | 2005-08-17 | Method for producing spheroidized inorganic powder |
| JP236450/2005 | 2005-08-17 | ||
| JP2006027240A JP2007204334A (en) | 2006-02-03 | 2006-02-03 | Method for production of spherical glass powder with improved electric insulation |
| JP2006027241A JP2007204335A (en) | 2006-02-03 | 2006-02-03 | Method for production of spherical glass powder with improved electric insulation |
| JP027241/2006 | 2006-02-03 | ||
| JP027240/2006 | 2006-02-03 | ||
| PCT/JP2006/315750 WO2007020855A1 (en) | 2005-08-17 | 2006-08-09 | Process for producing spherical inorganic particle |
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| CN101296874B CN101296874B (en) | 2011-02-02 |
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| CN103553304A (en) * | 2013-10-31 | 2014-02-05 | 河北勇龙邦大新材料有限公司 | Method and device for quickly sintering inorganic microspheres |
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| CN104445885B (en) * | 2014-10-30 | 2023-03-24 | 中国建材国际工程集团有限公司 | Water mist treatment method for hollow glass beads |
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Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3133821A (en) * | 1961-10-13 | 1964-05-19 | Standard Oil Co | Method of making silica insulating material |
| JPS63260832A (en) * | 1987-04-18 | 1988-10-27 | Sekisui Plastics Co Ltd | Production of fine spherical glass particle having uniform particle diameter |
| FR2619101A1 (en) * | 1987-08-05 | 1989-02-10 | Saint Gobain Vitrage | TECHNIQUE FOR THE PRODUCTION OF MICROSPHERES IN SILICA |
| NO177137B1 (en) * | 1993-09-06 | 1995-08-14 | Svein Olerud | Process for the preparation of spherical silica from olivine |
| JP4313924B2 (en) * | 2000-03-16 | 2009-08-12 | 電気化学工業株式会社 | Spherical silica powder and method for producing the same |
| JP2005029425A (en) * | 2003-07-14 | 2005-02-03 | Nippon Electric Glass Co Ltd | Method and device for producing glass bead |
-
2005
- 2005-08-17 JP JP2005236450A patent/JP4941629B2/en not_active Expired - Fee Related
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2006
- 2006-08-09 CN CN2006800297045A patent/CN101296874B/en not_active Expired - Fee Related
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Also Published As
| Publication number | Publication date |
|---|---|
| JP4941629B2 (en) | 2012-05-30 |
| JP2007051019A (en) | 2007-03-01 |
| CN101296874B (en) | 2011-02-02 |
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